The present invention relates to a fiber-reactive dyestuff, especially relates to a novel reactive formazan dyestuff.
United Kingdom Patent Publication 1,194,504 discloses formazan derivatives having the following formula: 
The fastness and dyeing properties of the said formazan derivatives are not good.
U.S. Pat. No. 4,607,098 discloses compounds of the following formula which exhibit improved fastness but with poor dyeing properties 
and fastness to chlorinated water.
U.S. Pat. No. 5,858,026 discloses formazan derivatives having the following formula: 
The above formazan derivatives still display poor dyeing properties.
The present invention provides novel reactive formazan dyestuffs of the following formula (I): 
wherein:
A is phenyl or naphthyl having 1 to 4 substituent groups, said substituent groups are selected from the group consisting of halogen, C1-4 alkyl, C1-4 alkoxyl, nitro, amino, hydroxyl, carboxyl, phosphonic acid and sulfo group, and wherein at least one substituent group is a sulfo group, said sulfo group is in the position ortho to the N-atom of hydrazone compound; preferably A is phenyl having 1 to 4 substituent groups;
B is a straight or branched C1-8 alkyl, or a phenyl, naphthyl or heteroaromatic group having 0 to 3 substituent groups, said substituent groups are selected from the group consisting of halogen, C1-4 alkyl, C1-4 alkoxyl, nitro, amino, hydroxyl, carboxyl, phosphonic acid and sulfo group, said heteroaromatic group is selected from the group consisting of: furan, thiophene, pyrrole, imidazole, pyrazole, pyridine, pyrimidine, quinoline, or benzimidazole; preferably B is phenyl having 0 to 3 substituent groups;
G is a phenyl or naphthyl having 0 to 3 substituent groups, said substituent groups are selected from the group consisting of halogen, C1-4 alkyl, C1-4 alkoxyl, nitro, amino, hydroxyl, carboxyl, phosphonic acid and sulfo group; preferably G is phenyl having 0 to 3 substituent groups;
Q is xe2x80x94NHCN, xe2x80x94OH, xe2x80x94SCH2COOH or 3-carboxypyridinium;
D is a phenyl or naphthyl having 0 to 3 substituent groups, said substituent groups are selected from the group consisting of halogen, C1-4 alkyl, C1-4 alkoxyl, nitro, amino, hydroxyl, carboxyl, phosphonic acid and sulfo group; preferably D is phenyl having 0 to 3 substituent groups;
Me is Cu, Ni or Co metal ion; preferably Me is Cu metal ion;
R is H, C1-8 alkyl, or C1-8 alkyl having at least one substituent group, said substituent group is selected from the group consisting of hydroxyl, carboxyl, sulfo, carbamoyl, and methoxy carbonyl; preferably R is H, C1-4 alkyl;
Z is xe2x80x94SO2xe2x80x94Y, xe2x80x94CONHxe2x80x94(CH2)hxe2x80x94SO2xe2x80x94Y, xe2x80x94(O)pxe2x80x94(CH2)gxe2x80x94CONHxe2x80x94(CH2)hxe2x80x94SO2xe2x80x94Y, or xe2x80x94NHxe2x80x94COxe2x80x94T; Y is xe2x80x94CHxe2x95x90CH2, or xe2x80x94CH2xe2x80x94CH2xe2x80x94U; U is xe2x80x94OSO3H, Cl, Br, xe2x80x94OPO3H2, xe2x80x94SSO3H or 
xe2x80x83T is xcex1, xcex2-halopropionyl or xcex1-haloacryloyl; g and h independently are an integer from 1 to 6;
P is the number 0 or 1; preferably Z is xe2x80x94SO2xe2x80x94Y or xe2x80x94NHxe2x80x94COxe2x80x94T, and Y is xe2x80x94CHxe2x95x90CH2, or xe2x80x94CH2xe2x80x94CH2xe2x80x94OSO3H, and T is xcex1, xcex2-halopropionyl or xcex1-haloacryloyl.
The compounds of the general formula (I) according to the present invention can be present in the acid form or in the form of their salts, in particular the alkali and alkaline earth metal salts. They find use, preferably in the form of the alkali metal salts, for dyeing and printing hydroxy and/or amide containing materials, in particular fiber materials.
The formula (I) dyestuff of the present invention is preferably the following formula (Ia) dyestuff, 
wherein
B is a straight or branched C1-8 alkyl, or a phenyl, naphthyl or heteroaromatic group having 0 to 3 substituent groups, said substituent groups are selected from the group consisting of halogen, C1-4 alkyl, C1-4 alkoxyl, nitro, amino, hydroxyl, carboxyl, phosphonic acid and sulfo group, said heteroaromatic group is selected from the group consisting of: furan, thiophene, pyrrole, imidazole, pyrazole, pyridine, pyrimidine, quinoline, or benzimidazole; preferably B is phenyl having 0 to 3 substituent groups;
Q is xe2x80x94NHCN, xe2x80x94OH, xe2x80x94SCH2COOH or 3-carboxypyridinium;
D is a phenyl or naphthyl having 0 to 3 substituent groups, said substituent groups are selected from the group consisting of halogen, C1-4 alkyl, C1-4 alkoxyl, nitro, amino, hydroxyl, carboxyl, phosphonic acid and sulfo group; preferably D is phenyl having 0 to 3 substituent groups;
R is H, C1-8 alkyl, or C1-8 alkyl having at least one substituent group, said substituent group is selected from the group consisting of hydroxyl, carboxyl, sulfo, carbamoyl, and methoxy carbonyl; preferably R is H or C1-4 alkyl;
Z is xe2x80x94SO2xe2x80x94Y, xe2x80x94CONHxe2x80x94(CH2)hxe2x80x94SO2xe2x80x94Y, xe2x80x94(O)pxe2x80x94(CH2)gxe2x80x94CONHxe2x80x94(CH2)hxe2x80x94SO2xe2x80x94Y, or xe2x80x94NHxe2x80x94COxe2x80x94T; Y is xe2x80x94CHxe2x95x90CH2, or xe2x80x94CH2xe2x80x94CH2xe2x80x94U; U is xe2x80x94OSO3H, Cl, Br, xe2x80x94OPO3H2, xe2x80x94SSO3H or 
xe2x80x83T is xcex1, xcex2-halopropionyl or xcex1-haloacryloyl; g and h independently are an integer from 1 to 6; P is the number 0 or 1; preferably Z is xe2x80x94SO2xe2x80x94Y or xe2x80x94NHxe2x80x94COxe2x80x94T, Y is xe2x80x94CHxe2x95x90CH2, or xe2x80x94CH2xe2x80x94CH2xe2x80x94OSO3H, T is xcex1, xcex2-halopropionyl or xcex1-haloacryloyl.
The formula (I) dyestuff of the present invention is also preferably the following formula (Ib) dyestuff, 
wherein
Q is xe2x80x94NHCN, xe2x80x94OH, xe2x80x94SCH2COOH or 3-carboxypyridinium;
R is H, C1-4 alkyl; preferably R is H;
Z is xe2x80x94SO2xe2x80x94Y; Y is xe2x80x94CHxe2x95x90CH2 or xe2x80x94CH2xe2x80x94CH2xe2x80x94U; U is xe2x80x94OSO3H, Cl or Br; preferably Z is xe2x80x94SO2xe2x80x94CH2xe2x80x94CH2xe2x80x94OSO3H.
The formula (I) dyestuff of the present invention is also preferably the following formula (Ic), (Id) or (Ie) dyestuff, 
wherein Q, R, D, and Z are define as the formula (Ia) dyestuff of the above. 
wherein Q, R, D, and Z are defined as the formula (Ia) dyestuff of the above. 
wherein Q, R, D, and Z are defined as the formula (Ia) dyestuff of the above.
The present invention is also related to the process for dyeing and printing cellulosic fiber materials (for example, cotton), which comprises treating the fiber materials with the formula (I) dyestuff in aqueous solution.
The formula (I) dyestuffs of the present invention can be synthesized by the following reaction step (a) to step (c).
Step (a):
The compound of the formula (III) is reacted with 1,3,5-trihalogen triazine of the following formula (IV) to obtain the following formula (V) compound, 
wherein Hal is xe2x80x94F, xe2x80x94Cl, xe2x80x94Br; A, B, G, and Me are defined as the formula (I) dyestuff of the above. The reaction is carried out in aqueous solution at a temperature between 0 to 30xc2x0 C., and below 20xc2x0 C. is preferred. The acid generated in the reaction is neutralized by adding an acid-binding agent, and the pH is controlled between 1 to 4. Upon completion the reaction, the product of the above formula (V) can be obtained.
Step (b):
The compound of the formula (V) is reacted with the following formula (VI) compound to obtain the following formula (VII) compound, 
wherein Hal is xe2x80x94F, xe2x80x94Cl, xe2x80x94Br; A, B, G. and Me are defined as the formula (I) dyestuff of the above. The reaction temperature is controlled between 20 to 80+ C., and 40 to 60xc2x0 C. is preferred. The acid generated in the reaction is neutralized by adding an acid binding agent. The pH is controlled between 4 to 12, and 7 to 10 is preferred. Upon completion the product of formula (VII) is obtained
Step (c):
After the above reaction is completed, the compound of the following formula (VIII) 
wherein R, D, and Z are defined as the above, is then added to the solution of the compound of formula (VII). The reaction temperature is controlled between 30 to 80xc2x0 C., and 40 to 60xc2x0 C. is preferred. The acid generated in the reaction is neutralized by adding an acid binding agent. The pH is controlled between 2 to 6, and 3 to 5 is preferred. Upon completion of the reaction, formazan derivatives represented by the above formula (I) dyestuff can be obtained.
In the above reaction steps (a) to (c), the formula (III) and (IV) and (VI) and (VIII) compounds each approximately one molar equivalent, can be reacted with one another in any sequence to yield the formazan derivatives represented by the above formula (1) dyestuff.
The preparation of the formula (III) compound is described in U.S. Pat. No. 5,858,026.
The formula (III) compound can be produced by diazotating an amine compound of the following formula (X) compound, then hydrolyzing the obtained compound in the presence of inorganic acid to give hydrazine compound, reacting the obtained compound with the aldehyde compound of the following formula (XI) to synthesize hydrazone compound, reacting the obtained compound with the compound of the formula (XII) to diazotate it, and then coupling them in the presence of metal ion to give the formula (XIII) compound, 
wherein P is nitro group or acetylamino group, and the definetion of A, B, G, and Me are same as those of the above formula (I). The formula (III) compound can be produced by reduction of nitro group or hydrolysis of acetylamino group of the formula (XIII) compound.
Metal ion used in this process are sulfate, carbonate, acetate, salilate, tartarate or chloride which concerns in the reaction.
Examples of the above formula (X) compound are: aniline-2-sulfonic acid, aniline-2,4-disulfonic acid, aniline-2,5-disulfonic acid, 4-methylaniline-2-sulfonic acid, ) 5-methylaniline-2-sulfonic acid, 3,4-dimethylaniline-2-sulfonic acid, 4,5-dimethylaniline-2-suffonic acid, 2-methylaniline-4,6-disulfonic acid, 4-methylaniline-2,5-disulfonic acid, 4-methoxyaniline-2-sulfonic acid, 5-methoxyaniline-2-sulfonic acid, 4-methoxy-5-chloroaniline-2-suflfonic acid, 4,5-dimethoxyaniline-2-sulfonic acid, 4-ethoxyaniline-2-sulfonic acid. 5-ethoxyaniline-2-sulfonic acid, 4-hydroxyaniline-2-sulfonic acid, 5-hydroxyaniline-2-suffonic acid, 5-hydroxyaniline-2,4-disulfonic acid, 4-carboxylaniline-2-sulfonic acid, 5-carboxylaniline-2-sufonic acid, 4-hydroxy-3-carboxylaniline-2-sulfonic acid, 4-nitroaniline-2-sulfonic acid, 5-nitroaniline-2-sulfonic acid, 2,4-dinitroaniline-6-sulfonic acid, 5-nitro-4-chloroaniline-2-sulfonic acid, 4-fluoroaniline-2-sulfonic acid, 3-chloroaniline-2-sulfonic acid, 4-chloroaniline-2-sulfonic acid, 5-chloroaniline-2-sulfonic acid, 4,5-dichloroaniline-2-sulfonic acid, 2,4-dichloroaniline-6-sulfonic acid, 2,4,5-trichloroaniline-6-sulfonic acid, 4-chloro-5-carboxyaniline-2-sulfonic acid, 2,5-dichloro-4-nitroaniline-6-sulfonic acid, 4-bromoaniline-2-sulfonic acid, 5-bromoaniline-2-sulfonic acid, 2,4-dibromoaniline-6-sulfonic acid, 3,4-dibromoaniline-6-sulfonic acid, 4-iodoaniline-2-sulfonic acid, 5-iodoaniline-2-sulfonic acid, 4-acetaminoaniline-2-sulfonic acid, 5-acetaminoaniline-2-sulfonic acid, 1,4-phenylenediamine-2,5-disulfonic acid, 1,3-phenylenediamine-4,6-disulfonic acid, 1-naphthylamine-2-sulfonic acid, 2-naphthylamine-1-sulfonic acid, 1-naphthylamine-2,4-disulfonic acid, 1-naphthylamine-2,5-disulfonic acid, 2-naphthylamine-1,5-disulfonic acid, 2-naphthylamine-1,7-disulfonic acid, 2-naphthylamine-3,6-disulfonic acid, 2-naphthylamine-3,7-disulfonic acid, 1-naphthylamine-2,4,7-trisulfonic acid, 2-naphthylamine-3,6,8-trisulfonic acid, 2-naphthylamine- 1,5,7-trisulfonic acid.
Examples of the above formula (XI) compound are: benzaldehyde, 2-methoxybenzaldehyde, 3-methoxybenzaldehyde, 4-methoxybenzaidehyde, 4-methoxybenzaldehyde-3-sulfonic acid, 4-methoxy-3-chlorobenzaldehyde, 2-nitrobenzaldehyde, 3-nitrobenazldehyde, 2-hydroxybenzaldehyde, 2-chlorobenzaldehyde, 4-chlorobenzaldehyde, 2,4-dichlorobenzaldehyde, 2-chlorobenzaldehyde-5-sulfonic acid, benzaldehyde-2-sulfonic acid, benzaldehyde-3-sulfonic acid, benzaldehyde-4-sulfonic acid, benzaldehyde-2,4-disulfonic acid, 2-acetylaminobenzaldehyde, 4-acetylaminobenzaldehyde, 4-nitrobenzaldehyde-2-sulfonic acid, 3-methyl-2-nitrobenzaldehyde, 3-methy-6-nitrobenzaldehyde, 2-chloro-6-nitrobenzaldehyde, 1-naphthoaldehyde, 2-naphthoaldehyde, furan-2-aldehyde, thiophene-2-aldehyde, pyrrole-2-aldehyde, imidazole-2-aldehyde, pyrozole-5-aldehyde, pyridine-2-aldehyde, pyridine-3-aldehyde, pyridine-4-aldehyde, pyrimidine-5-aldehyde, quinoline-4-aldehyde, benzimidazole-2-aldehyde, acetaldehyde, butylaldehyde, heptaldehyde, acrylaldehyde, crotonaldehyde, phenacetaldehyde, cinnamaldehyde.
Examples of the above formula (XII) compound are: 2-aminophenol, 4-methyl-2-aminophenol, 5-methyl-2-aminophenol, 4-sulfo-2-aminophenol, 5-sulfo-2-aminophenol, 4-methoxy-2-aminophenol, 5-methylsulfonyl-2-aminophenol, 4-methylsulfamoyl-2-aminophenol, 1,4-dimethylsulfamoyl-2-aminophenol, 5-nitro-2-aminophenol, 4-bromo-2-aminophenol, 4,6-disulfo-2-aminophenol, 2-acetylamino-6-aminophenol-4-sulfonic acid, 6-nitro-4-sulfo-2-aminophenol, 4-nitro-6-suffo-2-aminophenol, 4-acetylamino-6-sulfo-2-aminophenol, 4-chloro-6-sulfo-2-aminophenol, 6-chloro-4-sulfo-2-aminophenol, 4-methylsulfonyl-2-aminophenol, 4-butyl sulfonyl-2-aminophenol, 4-ethylsulfonyl-2-aminophenol, 4-sulfamoyl-2-aminophenol, 1-amino-2-hydroxynaphthalene-4,6-desulfonic acid, 1-amino-2-hydroxy-6-chloronaphthalene-4-sulfonic acid, 4-methylol-6-sulfo-2-aminophenol.
The above formula (VIII) compound can be synthesised by reacting the following formula (XIV) compound with an alkylation reagent.
H2Nxe2x80x94Dxe2x80x94Zxe2x80x83xe2x80x83(XIV)
Examples of the alkylation reagents are: alkylhalide, dialkylsulfate, monosubstituted ethylene, or oxide. Examples of the alkylhalide are methylchloride, ethylchloride, n-propylchloride, isopropylchloride, n-buthylchloride, isobuthylchloride, sec-buthylchloride, methylbromide, ethylbromide, n-propylbromide, isopropylbromide, n-buthylbromide, isobuthylbromide, sec-buthylbromide.
Examples of the dialkylsulfate are: dimethylsulfate, diethylsulfate, dipropylsulfate. Examples of the monosubstituted ethylene are: acrylonitrile, acrylic acid, methylacrylate, ethylacrylate, acrylamide, vinylsulfonic acid. Examples of the oxide are: ethyleneoxide, propyleneoxide, glycol, trimethyleneoxide, xcex2-buthyloxide, 2-methyl-a-buthyleneoxide, 2-ethyl-3-methyleneoxide, methoxyethyleneoxide, or n-buthoxyleneoxide.
Examples of theformula (XIV) compound are: 1-aminobenzene-2,3-xcex2-sulfatoethylsulfone, 1-aminobenzene-2,4-xcex2-sulfatoethylsulfone, 1-aminobenzene-3-phosphatoethylbenzene, 1-amino-4-methylbenzene-3-xcex2-sulfatoethylsulfone, 1-aminobenzene-3-xcex2-chloroethylsulfone, 1-amino-4-methoxybenzene-3-xcex2-sulfatoethylsulfone, 1-amino-2,5-dimethylbenzene-4-xcex2-sulfatoethylsulfone, 1-amino-2-methoxybenzene-4-xcex2-sulfatoethylsulfone, 1-amino-2-chlorobenzene-4-xcex2-sulfatoethylsulfone, 1-amino-4-methoxybebzene-5-xcex2-sulfatoethylsulfone, 2-aminonaphthalene-8-xcex2-sulfatoethylsulfone-6-sulfonic acid, 2-aminonaphthalene-8-xcex2-sulfatoethylsulfone, 1-amino-2,5-dimethoxybenzene-4-vinylsulfone, 1-amino-2-methoxy-5-methylbenzene-4-xcex2-sulfatoethylsulfone, 2-aminonaphthalene-4,5,6-xcex2-sulfatoethylsulfone, 2-aminonaphthalene-4,5,7-xcex2-sulfatoethylsulfone, 1-amino-2-bromobenzene-4-vinylsulfone, 2-amino-8-sulfonaphthalene-6-xcex2-sulfatoethylsulfone, 2-aminonaphthalene-8-xcex2-phhosphatoethylsulfone-6-sulfonic acid, 2-aminonaphthalene-8-vinylsulfone-6-sulfonic acid, 1-amino-2-methoxy-5-methylbenzene-4-xcex2-chloroethylsulfone, 1-aminobenzene-2,3-vinylsulfone, 1-aminobenzene-2,4-vinylsulfone, 1-amino-2-methoxy-5-chlorobenzene-4-xcex2-chloroethylsulfone, 1-amino-2-methoxy-5-chlorobenzene-4-vinylsulfone, 1-amino-2-ethoxy-5-chlorobenzene-4-xcex2-chloroethylsulfone, 1-amino-2-ethoxy-5-chlorobenzene-4-vinylsulfone, 2-aminonaphthalene-8-xcex2-sulfatoethylsulfone-1-sulfonic acid, 5-chloroaniline-2-xcex2-sulfatoethylsulfone, 5-sulfoaniline-2-xcex2-sulfatoethylsulfone, aniline-2-xcex2-phosphatoethylsulfone, 5-chloroaniline-2-xcex2-phosphatoethylsulfone, 5-chloroaniline-2-vinylsulfone, 5-sulfoaniline-2-vinylsulfone, aniline-2-xcex2-chloroethylsulfone, 5-chloroaniline-2-xcex2-chloroethylsulfone, 5-sulfoaniline-2-xcex2-chloroethylsulfone, aniline-2-xcex2-thiosulfatoethylsulfone, 5-chloroaniline-2-xcex2-thiosulfatoethylsulfone, 5-sulfoaniline-2-xcex2-thiosulfatoethylsulfone, 3-Amino-2xe2x80x2-(2-sulfatoethylsulfonyl)ethylbenzamide, 4-Amino-2xe2x80x2-(2-sulfatoethylsulfonyl)ethylbenzamide, 2-amino-5-[(2-bromo-1-oxo-2-propenyl)amino]-1-benzenesulfonic acid, 2-amino-5-[(2,3-dibromopropionyl)amino]-1-benzenesulfonic acid, 2-amino-4-[(2-bromo-1-oxo-2-propenyl)amino]-1-benzenesulfonic acid, 2-amino-4-[(2,3-dibromopropionyl)amino]-1-benzenesulfonic acid.
Suitable acid binding agents include alkali metal hydroxides, alkali metal carbonates, or alkali metal bicarbonates. The hydroxides, carbonates, or bicarbonates of sodium, potassium, or lithium are valuable, and particularly sodium carbonates or bicarbonates are most valuable.
The dyestuffs of the present invention can be produced by the above methods, reaction conditions are fully described in the above description. The dyestuffs of the present invention can be purified by known processes such as spray drying, precipitation, or filtration. They can be in the form of powder, granules, particle or liquid and an auxiliary reagent, for example, retarding agent, leveling agent, assistant agent, surfactant agent, or dispersing agent may be added.
The dyestuffs of the present invention all contain at least one anionic group, such as a sulfonyl group. For convenience they are expressed as free acid in the specification. When the dyestuffs of the present invention are manufactured, purified or used, they often exist in the form of water soluble salt, especially the alkaline metallic salts, such as the sodium salt, lithium salt, potassium salt or ammonium salt, preferably sodium salt.
The dyes of the present invention are distinguished by high fixation and very good build-up. They are also distinguished by low substantivity and high exhaustion, and they are suitable for dyeing and printing of materials containing either cellulose fibers, such as cotton, synthetic cotton, hemp, and synthetic hemp. Materials of high light and wet fastness can be obtained. Also materials of good fastness to other agencies can be obtained
The following examples illustrate the present invention, however, the present invention is not limited by these examples. The compounds are depicted as being in the free acid form although in reality they are usually in the form of metal salts such as alkali metal salts, in particular, the sodium salts.
The Examples that follow serve to illustrate the invention. Parts and percentages are by weight, unless otherwise stated. Parts by weight bear the same relation to parts by volume as the kilogram to the liter. The compounds written in the form of formulae are shown in the form of free acids; in general, they are prepared and isolated in the form of their alkali metal salts and used for dyeing in the form of their salts. In the same way it is possible to use the starting compounds and components mentioned in the form of free acids in the examples below in particular the Table of examples, in the synthesis as such or in the form of their salts, preferably alkali metal salts.
The absorption maxima (xcex max) in the visible region reported for the compounds according to the present invention were determined from aqueous solutions of alkali metal salts.